Dielectric composition for high frequencies

ABSTRACT

A dielectric composition for high frequencies, which comprises a ceramic component comprising Sr x  (Ni 1/3  Nb 2/3 ) y  O 3  (x/y=0.96-1.06), a ceramic component comprising Sr x  (Ni 1/3  Nb 2/3 ) y  O 3  (x/y=0.96-1.06) as the main constituent and one or more minor constituents which are selected from the group consisting of TiO 2 , SrTiO 3  and CaTiO 3  (TiO 2  ≦25% by mole, SrTiO 3  ≦6.5% by mole, and CaTiO 3  ≦13.3% by mole), or a ceramic component comprising Sr x  (Ni 1/3  Nb 2/3 ) y  O 3  (x/y=0.96-1.06) and Ba(M II   1/3  M v   2/3 )O 3  (M II  is Ni, Mg or Zn, and M v  is Nb or Ta, provided that M II  =Ni, Mg or zn when M v  =Nb, and M II  =Mg or Zn when M v  =Ta) , and 0.1-50% by weight of glass added to the ceramic component.

FIELD OF THE INVENTION

The present invention relates to a dielectric composition for high frequencies which is useful to provide dielectrics for constructing elements which are used in high-frequency circuits.

DESCRIPTION OF THE RELATED ART

The use of multi-layer devices is effective in downsizing and increasing the reliability of parts such as filters which are used in high-frequency circuits. The materials used for preparing multi-layer devices for such applications are required to have reasonable relative permittivities and high Q (in other words, less dielectric loss), and to be capable of being fired at 1,000° C. or below, more specifically, of being satisfactorily.densified by firing at 1,000° C. or below, since they must be fired together with Cu and/or an Ag/Pd conductor.

Dielectrics hitherto developed and used for high frequencies which can be fired at 1,000° C. or below include

1) BaO-Al₂ O₃ -B₂ O₃ -SiO₂ -or BaO-SrO-ZrO₂ -SiO₂ --based glass materials;

2) Pb-containing perovskite-based materials;

3) Bi-containing materials; and

4) Ceramic-glass composite materials.

The conventional materials mentioned above have the following problems. Specifically, use of the Pb-containing perovskite-based or Bi-containing materials results in variation in composition due to evaporation of the components during firing, and this prevents the manufacture of products having a uniform composition. On the other hand, the BaO-Al₂ O₃ -B₂ O₃ -SiO₂ -or BaO-SrO-ZrO₂ -SiO₂ --based glass materials, and the ceramic-glass composite materials have relative permittivities as low as ε=6, and ε=14, respectively, and further their values of Q are as relatively small as approximately 1,000 (1 MHz).

Here, dielectric compositions for high frequencies which are used in dielectric resonators and so on must have temperature coefficients τ_(f) of resonance frequencies which are close to 0 ppm/°C., whereas dielectric compositions for high frequencies which are used as capacitor materials must have temperature coefficients τε of relative permittivities which roughly satisfy the relationship: -60 ppm/°C. ≦τε≦60 ppm/°C. (CH properties).

OBJECT AND SUMMARY OF THE INVENTION

It is an object of the present invention to provide a dielectric composition for high frequencies, free of the problems of the prior art mentioned above, which is useful as a material for preparing multi-layer devices which are effective in downsizing and increasing the reliability of elements for use in high-frequency circuits, both the relative permittivity and the Q of which are high, and which can be fired at 1,000° C. or below.

It is another object of the present invention to provide a high-performance dielectric composition for high frequencies, both the relative permittivity and the Q of which are high, which can be fired at 1,000° C. or below, and which has a small absolute value of the temperature coefficient τf of the resonance frequency and the temperature coefficient τε of the relative permittivity.

The dielectric composition for high frequencies according to a first embodiment of the present invention is characterized by the addition of 0.1-50% by weight of glass to a ceramic component comprising Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (wherein x/y=0.96-1.06).

The addition of 0.1-50% by weight of glass to the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ allows firing at 1,000° C. or below without decreasing the Q and the ε.

The dielectric composition for high frequencies according to a second embodiment of the present invention is characterized by the addition of 0.1-50% by weight of glass to a ceramic component comprising Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (wherein x/y=0.96-1.06) as the main constituent and one or more minor constituents which are selected from the group consisting of TiO₂, SrTiO₃ and CaTiO₃, wherein TiO₂ comprises 25% by mole or less, SrTiO₃ comprises 6.5% by mole or less, and CaTiO₃ comprises 13.3% by mole or less of the ceramic component.

According to the second embodiment, addition of a predetermined proportion of one or more materials which are selected from the group consisting of TiO₂, SrTiO₃ and CaTiO₃ to a Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ ceramic-glass composite material, particularly a Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ ceramic-(MgO-BaO-B₂ O₃ -SiO₂) glass composite material, provides a dielectric composition which has desired values of τ_(f) and τε within the range: -40 ppm/°C. ≦τ_(f) ≦20 ppm/°C. (-60 ppm/°C.≦τε≦60 ppm/°C.), while satisfying the following equation:

    τ.sub.f =-τε/2-α(α:coefficient of linear expansion of the material=10 ppm/°C.)

The dielectric composition for high frequencies according to a third embodiment of the present invention is characterized by the addition of 0.1-50% by weight of glass to a ceramic component comprising Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (wherein x/y=0.96-1.06) and Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ (wherein M^(II) is Ni, Mg or Zn, and M^(v) is Nb or Ta, provided that M^(II) is Ni, Mg or Zn when M^(v) is Nb, and M^(II) is Mg or Zn when M^(v) is Ta) .

It is possible to solve the problems of the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ ceramic-(MgO-BaO-B₂ O₃ -SiO₂) glass composite material and thus to provide a high-performance dielectric composition for high frequencies which has a temperature coefficient τ_(f) of the resonance frequency which is close to 0 ppm/°C., and a temperature coefficient τε of the relative permittivity which satisfies the relationship: -60 ppm/°C.≦τε≦60 ppm/°C., by further compounding the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ ceramic-glass composite material, particularly the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ ceramic-(MgO-BaO-B₂ O₃ -SiO₂) glass composite material, with the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ (wherein M^(II) is Ni, Mg or Zn, and M^(v) is Nb or Ta, provided that M^(II) is Ni, Mg or Zn when M^(v) is Nb, and M^(II) is Mg or Zn when M^(v) is Ta).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will now be described in detail.

The dielectric composition for high frequencies according to the present invention is prepared by adding 0.1-50% by weight of glass to a specific ceramic component.

Therefore, an explanation will be first given regarding the ceramic component of a ceramic-glass composite-base dielectric composition for high frequencies according to the present invention.

The ceramic component of the dielectric composition for high frequencies according to the first embodiment is Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (wherein x/y=0.96-1.06).

According to the present invention, when the dielectric composition is fired in an atmosphere of nitrogen, the x/y ratio of the ceramic component Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ is preferred to be 0.96-1.06. The Q of the resulting dielectric remarkably decreases when the value is lower than 0.96 or exceeds 1.06.

In contrast, when the dielectric composition is fired in the air, the x/y ratio of the ceramic component Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ is preferred to be 0.96-1.01. The Q of the resulting dielectric remarkably decreases when the alue is lower than 0.96 or exceeds 1.01.

The ceramic component according to the second embodiment comprises a main constituent represented by Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (wherein x/y=0.96-1.06), and one or more minor constituents which are selected from the group consisting of TiO₂, SrTiO₃ and CaTiO₃, wherein

TiO₂ ≦25% by mole

SrTiO₃ ≦6.5% by mole, and

CaTiO₃ ≦13.3% by mole

According to the second embodiment, the proportions of the minor constituents of the ceramic component which exceed the ranges mentioned above lead to the excessive presence of the minor constituents, and this undesirably results in τ_(f) >20 and τε<-60.

The proportions of the minor constituents of the ceramic component are preferred to be 20% by mole or less in total.

The ceramic component according to the third embodiment comprises Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (wherein x/y=0.96-1.06) and Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ (wherein M^(II) is Ni, Mg or Zn, and M^(v) is Nb or Ta, provided that M^(II) is Ni, Mg or Zn when M^(v) is Nb, and M^(II) is Mg or Zn when M^(v) is Ta).

According to the third embodiment, the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ and the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ which constitute the ceramic component are preferably compounded at the molar ratio of Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ :Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ =(1-α):α (wherein 0 <α≦0.8), that is, so as to provide a ceramic composition represented by (1-α) Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ ·αBa(M^(II) _(1/3) M^(v) _(2/3))O₃ (0 <α≦0.8). Here, when the value of α exceeds 0.8, the proportion of the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ increases excessively and impairs the effects of the present invention which result from the further compounding of the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ --glass composite material with the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃, thus failing to give preferable values of τ_(f) and τε. The preferable values of α are as follows depending on the relationship with the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃.

In cases where the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ is Ba(Ni_(1/3) Nb_(2/3))O₃ : 0<α≦0.8,

in cases where the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ is Ba(Mg_(1/3) Nb_(2/3))O₃ : 0<α≦0.34,

In cases where the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ is Ba(Zn_(1/3) Nb_(2/3))O₃ : 0<α≦0.33,

in cases where the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ is Ba(Mg_(1/3) Ta_(2/3))O₃ : 0<α≦0.73, and

in cases where the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ is Ba(Zn_(1/3) Ta_(2/3))O₃ : 0<α≦0.76.

According to the first through the third embodiments, the addition of glass to the ceramic coponent descried above in a proportion less than 0.1% by weight fails to achieve satisfactory densification by firing at 1,000° C. or below, and thus results in a lower Q. The addition of more than 50% by weight of glass to the ceramic component results in a relatively lower content of the ceramic component, and this results in a decrease in the dielectric coefficient and the Q.

When glass is added to the ceramic component in a proportion of 1-40% by weight, particularly 2-30% by weight, according to the present invention, a dielectric composition for high frequencies is provided with significantly increased dielectric coefficient and Q, and also with excellent τ_(f) and τε according to the second and the third embodiments thereof.

Here, according to the present invention, the glass preferably is MgO-BaO-B₂ O₃ -SiO₂ --based glass, and the preferable composition thereof is as follows.

    ______________________________________                                         Composition of MgO--BaO--B.sub.2 O.sub.3 --SiO.sub.2 -based glass (weight      %)                                                                             ______________________________________                                                 MgO          20-50                                                             BaO           5-25                                                             B.sub.2 O.sub.3                                                                             15-30                                                             SiO.sub.2    10-25                                                     ______________________________________                                    

The dielectric composition for high frequencies according to the first embodiment can be easily prepared by mixing a ceramic component Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ which is prepared by mixing and calcinating oxides or carbonates of the metal elements which constitute the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃, for example, SrCO₃, NiO and Nb₂ O₅, in the proportions so as to provide the composition of the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃, with a predetermined proportion of glass added thereto, and such dielectric composition for high frequencies according to the present invention can be easily put into practical use by being formed with an appropriate binder added, and being fired in an atmosphere of nitrogen or in the air at 1,000° C. or below, for example, 950°-980° C. Here, the binder is removed in the air at 500°-600° C. prior to firing in cases where the firing is carried out in an atmosphere of nitrogen.

The dielectric composition for high frequencies according to the second embodiment can be easily prepared by mixing the main constituent Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ which is obtained by mixing and calcinating oxides or carbonates of the metal elements which constitute the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃, for example, SrCO₃, NiO and Nb₂ O₅, in the proportions so as to provide the composition of the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃, with the minor constituent TiO₂ or the minor constituent SrTiO₃ or CaTiO₃ which is obtained as described below, and further with a predetermined proportion of glass added thereto. The minor constituent SrTiO₃ is obtained by mixing and calcinating, for example, SrCO₃ and TiO₂, so as to provide the composition of SrTiO₃. The minor constituent CaTiO₃ is obtained by mixing and calcinating, for example, CaCO₃ and TiO₂, so as to provide the composition of CaTiO₃. Such dielectric compositions for high frequencies according to the present invention can be easily put into practical use by being formed with an appropriate binder added thereto, and fired at 1,000° C. or below, for example, 950°-980° C.

The dielectric composition for high frequencies according to the third embodiment can be easily prepared by measuring out the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ and the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ so as to provide a predetermined molar ratio, which are obtained by mixing and calcinating oxides or carbonates of the metal elements which constitute the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ and the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃, for example, SrCO₃, BaCO₃, NiO, Nb₂ O₅, MgO, ZnO and Ta₂ O₅, in the proportions so as to provide the compositions of the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ and the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃, respectively, and mixing the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ and Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ with a predetermined proportion of glass added thereto. Such a dielectric composition for high frequencies according to the present invention can be easily put into practical use by being formed with an appropriate binder added thereto, and fired at 1,000° C. or below, for exile, 950°-980° C.

Here, in cases where glass, for exile, MgO-BaO-B₂ O₃ -SiO₂ --based glass, is added, the glass is desired to be added as a glass frit prepared in advance, though the respective oxides in the same weight proportions as the glass component or substantial amounts of the carbonates can be added to andmixed with the ceramic component to concurrently achieve the vitrification and calcination during the process of heat treatment.

The present invention will now be explained more specifically with reference to the Examples.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a side elevational view of the entire apparatus.

FIG. 2 shows how the spreader plate with its motor is mounted.

FIG. 3 is an enlarged representation of how the tension cables are anchored.

FIGS. 4 and 5 show various parts for connecting the legs to the ring (FIG. 4) and to the struts (FIG. 5), respectively;

FIG. 6 is a side view of the hopper and the shutter;

FIG. 7 is a perspective view of the shutter;

FIGS. 8a, 8b, and 8c show details of the scatter disk;

FIG. 9 shows a trunco-conical embodiment of scattering disk;

FIG. 10 shows the disk of FIG. 9 installed below a hopper to stop the flow of material when the disk is stationary;

FIG. 11a shows an embodiment with a base disk and a scattering disk;

FIG. 11b shows the trunco-conical scattering disk of FIG. 11a.

EXAMPLES 1-9, AND COMPARATIVE EXAMPLES 1 AND 2

SrCO₃, NiO and Nb₂ O₅ were measured out in the stoichiometric proportions so as to provide Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (x/y=1), and crushed and mixed with 2-propanol as the dispersing medium in a ball mill for 24 hours, and the mixture was dried and then calcined in the air at 1,350° C. for 4 hours. The calcination product was again crushed and mixed with 2-propanol as the dispersing medium in the ball mill for 24 hours to synthesize Sr(Ni_(1/3) Nb_(2/3))O₃.

The resulting Sr(Ni_(1/3) Nb_(2/3))O₃ was mixed with a MgO-BaO-B₂ O₃ -SiO₂ -based glass (weight ratio of the constituents, MgO: BaO: B₂ O₃ : SiO₂ =45: 15: 25: 15) frit added thereto in the proportions indicated in. Table 1, and 25% by weight of a binder (5% by weight of an aqueous solution of polyvinyl alcohol) was added to each mixture to form a 15-mm-dia, 1.5-mm-thick pellet which was fired in the air at 980° C. for 1 hour.

The relative permittivities ε, Q and relative densities of the resulting specimens were measured, with the results shown in Table 1.

Here, the relative permittivities were measured at a frequency of 1 MHz, a voltage of 0.5 Vrms, and a temperature of 25° C., with an LF impedance analyzer model 4192A manufactured by YHP, Inc. The values of Q were measured at a frequency of 1 MHz, and a temperature of 25° C., with a Q meter model 4342A manufactured by YHP, Inc.

                  TABLE 1                                                          ______________________________________                                                       Amount of Relative       Relative                                              glass added                                                                              permittivity   density                                 Specimen      (wt. %)   (ε)                                                                              Q    (%)                                     ______________________________________                                         Comp. Ex.                                                                             1      0.05      14.5        950                                                                               80                                      Example                                                                               1      0.1       22.1      1,800                                                                               90                                             2      1         28.5      2,100                                                                               92                                             3      2         29.2      2,400                                                                               95                                             4      3         29.0      2,500                                                                               96                                             5      10        25.3      2,500                                                                               96                                             6      20        22.0      2,600                                                                               97                                             7      30        18.5      2,500                                                                               97                                             8      40        17.0      2,000                                                                               97                                             9      50        15.0      1,500                                                                               97                                      Comp. Ex.                                                                             2      55        12.2        850                                                                               97                                      ______________________________________                                    

Table 1 clearly shows the following facts.

Specifically, when the amount of glass added is less than 0.1% by weight (Comparative Example 1), the composition is not satisfactorily densified at the firing temperature of 980° C., and a satisfactory value of Q is not achieved. On the other hand, when the amount of glass added exceeds 50% by weight (Comparative Example 2), satisfactory values of Q and ε are not achieved due to the lower proportion of Sr(Ni_(1/3) Nb_(2/3))O₃.

In contrast, when glass is added at a rate of 0.1-50% by weight (Examples 1-9), particularly 1-40% by weight (Examples 2-8), and more particularly 2-30% by weight (Examples 3-7), satisfactory degrees of density are achieved by firing at 980° C., with higher levels of both Q and ε.

EXAMPLES 10-13, and Comparative Examples 3-5

Pellets were formed and fired in the air at 980° C. in the same manner as in Example 5, except that the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ was synthesized so as to have the x/y values indicated in Table 2 and the binder was added at a rate of 20% by weight.

The relative permittivities 8 and the values of Q of the resulting specimens were measured in the same manner as in Example 1, and the temperature coefficients τε of the relative permittivities thereof were concurrently investigated, with the results shown in Table 2.

Here, the temperature coefficients τε of the relative permittivities were calculated from the capacitances C₂₀ and C₈₅ measured at 20° C. and 85° C., respectively, according to the following equation:

    (C.sub.85 -C.sub.20)/C.sub.20 (85-20)×10.sup.6 (ppm/°C.)

                  TABLE 2                                                          ______________________________________                                                                        Temp. coef.                                                                    τε of                                               Relative       relative                                                        permittivity   permittivity                                    Specimen x/y    (ε)                                                                              Q    (ppm/°C.)                                                                       Remarks                                 ______________________________________                                         Comp.   3    0.94   25.2    1,400                                                                               60      Q decreased                           Ex.                                                                            Example                                                                               10    0.96   25.0    2,300                                                                               60                                                   11    0.98   25.1    3,000                                                                               60                                                   12    1.00   25.3    2,500                                                                               60                                                   13    1.01   25.2    2,000                                                                               60                                            Comp.   4    1.02   25.3      300                                                                               140     Q decreased,                          Ex.                                      and temp.                                                                      coef.                                                                          increased                                    5     1.04   25.4      250                                                                               200     Q decreased,                                                                   and temp.                                                                      coef.                                                                          increased                             ______________________________________                                    

As clearly shown in Table 2, x/y must be 0.96-1.01 when the firing is accomplished in the air.

EXAMPLES 14-19, and Comparative Example 6, 13

Pellets were formed in the same manner as in Example 5, except that the Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ was synthesized so as to have the x/y values indicated in Table 3 and the binder was added at a rate of 20% by weight. The obtained pellets were treated to remove the binder in the air at 600° C. for 4 hours, and then fired in an atmosphere of nitrogen at 980° C. for 1 hour.

The relative permittivities ε, the values of Q, and the temperature coefficients τε of the relative permittivities of the resulting specimens were measured in the same manner as in Example 10, with the results shown in Table 3.

                  TABLE 3                                                          ______________________________________                                                                        Temp. coef.                                                                    τε of                                               Relative       relative                                                        permittivity   permittivity                                    Specimen x/y    (ε)                                                                              Q    (ppm/°C.)                                                                       Remarks                                 ______________________________________                                         Example                                                                               14    0.96   25.0    3,500                                                                               60                                                   15    0.98   25.1    4,100                                                                               60                                                   16    1.00   25.0    4,200                                                                               60                                                   17    1.02   25.0    4,200                                                                               60                                                   18    1.04   24.9    3,900                                                                               60                                                   19    1.06   24.9    3,000                                                                               60                                            Comp.   6    1.08   24.9    1,900                                                                               80      Temp. coef.                           Ex.                                      increased                                    13    0.94   24.8    1,300                                                                               60      Q decreased                           ______________________________________                                    

As is apparent from Table 3, x/y must be 0.96-1.06 when the firing is accomplished in an atmosphere of nitrogen.

The results described above show that the dielectric composition for high frequencies according to the first embodiment of the present invention has high values of both Q and ε, and can be fired at 1,000° C. or below. Therefore, according to the first embodiment of the present invention, downsizing of and increasing the reliability of elements for use in high-frequency circuits can be effectively achieved by constructing high-performance multi-layer devices.

EXAMPLES 20-30, and Comparative Examples 7-9

SrCO₃, NiO and Nb₂ O₅ were measured out in the stoichiometric proportions so as to provide Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (x/y=1), and crushed and mixed with 2-propanol as the dispersing medium in a ball mill for 24 hours, then the mixture was dried and calcined in the air at 1,350° C. for 4 hours. The calcination product was again crushed and mixed with 2-propanol as the dispersing medium in the ball mill for 24 hours to synthesize Sr(Ni_(1/3) Nb_(2/3))O₃.

The resulting Sr(Ni_(1/3) Nb_(2/3))O₃ and TiO₂, SrTiO₃ or CaTiO₃, wherein SrTiO₃ and CaTiO₃ were obtained by crushing, mixing, drying, calcinating, crushing and mixing processes using TiO₂ or SrCO₃ or CaCO₃. and TiO₂ as the raw materials in the same manner as the above synthesis of Sr(Ni_(1/3) Nb_(2/3))O₃, were measured out in the proportions indicated in Table 4, a MgO-BaO-B₂ O₃ -SiO₂ -based glass (weight ratio of the constituents, MgO: BaO: B₂ O₃ : SiO₂ =45: 15: 25: 15) frit was added to the resulting ceramic component at a rate of 10% by weight, and 20% by weight of a binder (5% by weight of an aqueous solution of polyvinyl alcohol) was added to the mixture to form a 15-mm-dia, 1.5-mm-thick pellet which was fired in the air at 980° C. for 1 hour.

The temperature coefficients τ_(f) of the resonance frequencies and the temperature coefficients τε of the relative permittivities of the resulting specimens were measured, with the results shown in Table 4.

                                      TABLE 4                                      __________________________________________________________________________            Constituents of dielectric composition                                         (moles %)                    relative                                          Main constituent                                                                       Minor constituents                                                                        τ.sub.f                                                                         τ.sub.ε                                                                 permittivity                               Specimen                                                                              Sr(Ni.sub.1/3 Nb.sub.2/3)O.sub.3                                                       TiO.sub.2                                                                         SrTiO.sub.3                                                                        CaTiO.sub.3                                                                        (ppm/°C.)                                                                    (ppm/°C.)                                                                    (ε)                                                                          Q                                    __________________________________________________________________________     Example                                                                             20                                                                               91.7    8.3        -20    20 28.4  2,200                                     21                                                                               83.4    16.0          0 -20  31.9  2,100                                     22                                                                               75.0    25.0         20 -60  36.0  1,800                                Comp. Ex.                                                                            7                                                                               70.9    29.1         30 -80  38.1  1,600                                Example                                                                             23                                                                               97.8       2.2     -20    20 26.6  2,300                                     24                                                                               95.7       4.3        0 -20  27.9  2,100                                     25                                                                               93.5       6.5       20 -60  29.4  2,000                                Comp. Ex.                                                                            8                                                                               92.4       7.6       30 -80  30.1  1,500                                Example                                                                             26                                                                               95.6           4.4 -20    20 27.5  2,300                                     27                                                                               91.1           8.9    0 -20  29.9  2,100                                     28                                                                               86.7           13.3                                                                                 20 -60  32.5  2,000                                Comp. Ex.                                                                            9                                                                               84.5           15.5                                                                                 30 -80  33.9  1,700                                Example                                                                             29                                                                                89.27   8.05                                                                              1.79                                                                               0.89                                                                                 0 -20  28.7  2,100                                     30                                                                                86.61  11.65                                                                              0.87                                                                               0.87                                                                                 0 -20  29.5  2,000                                __________________________________________________________________________

The results described above clearly show that the dielectric composition for high frequencies according to the second embodiment of the present invention is a high-performance dielectric composition for high frequencies which has high values of both Q and ε, can be fired at 1,000° C. or below, and has preferable values of both the temperature coefficient τ_(f) of the resonance frequency and the temperature coefficient τε of the relative permittivity. Therefore, according to the second embodiment of the present invention, downsizing of and increasing the reliability of elements which are used in high-frequency circuits can be effectively achieved by constructing dielectric resonators or high-performance multi-layer devices as materials for preparing temperature-compensating capacitors.

EXAMPLES 31-60, and Comparative Example 10

SrCO₃, BaCO₃, NiO, Nb₂ O₅, MgO, ZnO and Ta₂ O₅ were measured out in the stoichiometric proportions so as to provide Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (x/y=1) and Ba (M^(II) _(1/3) M^(v) _(2/3)) O₃ (wherein M^(II) is Ni, Mg or Zn, and Mvis Nb or Ta) indicated in Table 5, respectively, and crushed andmixed with 2-propanol as the dispersing medium in a ball mill for 24 hours, and the mixtures were dried and then calcined in the air at 1,400° C. for 4 hours. The calcination products were again crushed and mixed with 2-propanol as the dispersing medium in the ball mill for 24 hours to synthesize. Sr(Ni_(1/3) Nb_(2/3))O₃ and Ba(M^(II) _(1/3) M^(v) _(2/3))O₃, respectively.

The resulting Sr(Ni_(1/3) Nb_(2/3))O₃ and Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ were measured out so as to provide the compositions of the ceramic component indicated in Table 5, and each was mixed with a MgO-BaO-B₂ O₃ SiO₂ -based glass (weight ratio of the constituents, MgO: BaO: B₂ O₃ : SiO₂ =45: 15: 25: 15) frit added thereto at a rate of 10% by weight, and 20% by weight of a binder (5% by weight of an aqueous solution of polyvinyl alcohol) was added to each mixture to form a 15-mm-dia, 1.5-mm-thick pellet which was fired in the air at 980° C. for 1 hour.

The temperature coefficients τ_(f) of the resonance frequencies and the temperature coefficients τε of the relative permittivities of the resulting specimens were measured, with the results shown in Table 5.

Table 5 clearly shows that the incorporation of the Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ improves the temperature coefficients τ_(f) of the resonance frequencies and the temperature coefficients τε of the relative permittivities.

                                      TABLE 5                                      __________________________________________________________________________            Composition of ceramic component                                               (1-α)Sr(Ni.sub.1/3 Nb.sub.2/3)O.sub.3 -                                  αBa(M.sup.II.sub.1/3 M.sup.v.sub.2/3)O.sub.3                                               τε                                                                      τ.sub.f                                      Specimen                                                                              Type of Ba(M.sup.II.sub.1/3 M.sup.v.sub.2/3)O.sub.3                                        Value of α                                                                     (ppm/°C.)                                                                     (ppm/°C.)                                __________________________________________________________________________     Example                                                                             31                                                                               Ba(Ni.sub.1/3 Nb.sub.2/3)O.sub.3                                                           0.05  10    -15                                                  32            0.1   -4    -8                                                   33            0.2   -20   0                                                    34            0.3   -30   5                                                    35            0.5   -42   11                                                   36            0.8   -60   20                                              Comp. Ex.                                                                           10            1     -68   24                                              Example                                                                             37                                                                               Ba(Mg.sub.1/3 Nb.sub.2/3)O.sub.3                                                           0.02  24    -22                                                  38            0.05  -6    -7                                                   39            0.1   -26   3                                                    40            0.2   -48   14                                                   41            0.3   -56   18                                                   42            0.34  -60   20                                                   43                                                                               Ba(Zn.sub.1/3 Nb.sub.2/3)O.sub.3                                                           0.02  26    -23                                                  44            0.05  2     -11                                                  45            0.1   -26   3                                                    46            0.2   -46   13                                                   47            0.3   -54   17                                                   48            0.33  -60   20                                                   49                                                                               Ba(Mg.sub.1/3 Ta.sub.2/3)O.sub.3                                                           0.05  24    -22                                                  50            0.1   -2    -9                                                   51            0.2   -32   6                                                    52            0.3   -46   13                                                   53            0.7   -58   19                                                   54            0.73  -60   20                                                   55                                                                               Ba(Zn.sub.1/3 Ta.sub.2/3)O.sub.3                                                           0.05  10    -15                                                  56            0.1   -4    -8                                                   57            0.2   -28   4                                                    58            0.4   -44   12                                                   59            0.7   -58   19                                                   60            0.76  -60   20                                              __________________________________________________________________________

EXAMPLES 61-63, and Comparative Examples 11 and 12

Specimens were prepared in the same manner as in Example 33, except that glass was added to 0.8Sr(Ni_(1/3) Nb_(2/3))₃ ·0.2Ba(Ni_(1/3) Nb_(2/3))O₃ at rates indicated in Table 6, and various properties of the respective specimens were investigated, with the results shown in Table 6. Here, the relative permittivities e and the values of Q were measured at 1 MHz.

                  TABLE 6                                                          ______________________________________                                                       Amount of Relative                                                                               Relative                                                     glass added                                                                              density permittivity                                   Specimen      (wt. %)   (%)     (ε)                                                                            Q                                      ______________________________________                                         Comp. Ex.                                                                             11     0.05      80      10.8      750                                  Example                                                                               61     0.1       90      18.2    1,600                                         62     1         92      23.3    1,900                                         63     40        97      13.3    1,800                                  Comp. Ex.                                                                             12     55        97       9.7      700                                  ______________________________________                                    

Table 6 clearly shows that the addition of glass to the ceramic component at a rate of 0.1-50% by weight, particularly 1-40% by weight, improves the properties.

The results described above clearly show that the dielectric composition for high frequencies according to the third embodiment of the present invention is a high-performance dielectric composition for high frequencies which has high values of both Q and ε, can be fired at 1,000° C. or below, and further has a temperature coefficient τ_(f) of the resonance frequency which is close to 0 ppm/°C., and a temperature coefficient τε of the relative permittivity which satisfies the relationship: -60 ppm/°C.≦τε≦60 ppm/°C. Therefore, according to the third embodiment of the present invention, downsizing of and increasing the reliability of elements which are used in high-frequency circuits can be effectively achieved by constructing dielectric resonators or high-performance multi-layer devices as materials for preparing capacitors. 

What is claimed is:
 1. A dielectric composition for high frequencies, which comprises a ceramic component comprising Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (wherein x/y=0.96-1.06), and 0.1-50% by weight of glass added thereto.
 2. A dielectric composition for high frequencies as claimed in claim 1, which is fired in an atmosphere of nitrogen.
 3. A dielectric composition for high frequencies as claimed in claim 1, which is fired in the air, and the x/y ratio of the ceramic component of which is 0.96-1.01.
 4. A dielectric composition for high frequencies as claimed in claim 1, wherein said glass consists mainly of MgO-BaO-B₂ O₃ -SiO₂, and said glass is added to said ceramic component at a rate of 1-40% by weight.
 5. A dielectric composition for high frequencies as claimed in claim 4, wherein said glass is MgO-BaO-B₂ O₃ -SiO₂ --based glass which contains 20-50% by weight of MgO, 5-25% by weight of BaO, 15-30% by weight of B₂ O₃, and 10-25% by weight of SiO₂, and said glass is added to said ceramic component at a rate of 2-30% by weight.
 6. A dielectric composition for high frequencies, which comprises a ceramic component comprising Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (wherein x/y=0.96-1.06) as the main constituent, and one or more minor constituents which are selected from the group consisting of TiO₂, SrTiO₃ and CaTiO₃, wherein TiO₂ comprises 25% by mole or less, SrTiO₃ comprises 6.5% by mole or less, and CaTiO₃ comprises 13.3% by mole or less of said ceramic component, and 0.1-50% by weight of glass added to said ceramic component.
 7. A dielectric composition for high frequencies as claimed in claim 6, wherein said glass consists mainly of MgO-BaO-B₂ O₃ -SiO₂, and said glass is added to said ceramic component at a rate of 1-40% by weight.
 8. A dielectric composition for high frequencies as claimed in claim 6, wherein the proportions of the minor. constituents of the ceramic component which are selected from the group consisting of TiO₂, SrTiO₃ and CaTiO₃ totals 20% by mole or less.
 9. A dielectric composition for high frequencies as claimed in claim 7, wherein said glass is MgO-BaO-B₂ O₃ -SiO₂ --based glass which contains 20-50% by weight of MgO, 5-25% by weight of BaO, 15-30% by weight of B₂ O₃, and 10-25% by weight of SiO₂, and said glass is added to said ceramic component at a rate of 2-30% by weight.
 10. A dielectric composition for high frequencies, which comprises a ceramic component comprising Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ (wherein x/y=0.96-1.06) and Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ (wherein M^(II) is Ni, Mg or Zn, and M^(v) is Nb or Ta, provided that M^(II) is Ni, Mg or Zn when M^(v) is Nb, and M^(II) is Mg or Zn when M^(v) is Ta), and 0.1-50% by weight of glass added to said ceramic component.
 11. A dielectric composition for high frequencies as claimed in claim 10, wherein the composition of said ceramic component is represented by (1-α)Sr_(x) (Ni_(1/3) Nb_(2/3))_(y) O₃ ·Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ (wherein M^(II) is Ni, Mg or Zn, and M^(v) is Nb or Ta, provided that M^(II) is Ni, Mg or Zn when M^(v) is Nb, and M^(II) is Mg or Zn when M^(v) is Ta), and α satisfies 0<α≦0./8.
 12. A dielectric composition for high frequencies as claimed in claim 10 wherein said glass consists mainly of MgO-BaO-B₂ O₃ -SiO₂, and said glass is added to said ceramic component at a rate of 1-40% by weight.
 13. A dielectric composition for high frequencies as claimed in claim 11, wherein said Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ is Ba(Ni_(1/3) Nb_(2/3))O₃, and 0<α<0.8.
 14. A dielectric composition for high frequencies as clawed in claim 11, wherein said Ba(M¹¹ _(1/3) M^(v) _(2/3))O₃ is Ba(Mg_(1/3) Nb_(2/3))O₃, and 0<α≦0.34.
 15. A dielectric composition for high frequencies as claimed in claim 11, wherein said Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ is Ba(Zn_(1/3) Nb_(2/3))O₃, and 0<α≦0.33.
 16. A dielectric composition for high frequencies as claimed in claim 11, wherein said Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ is Ba(Mg_(1/3) Ta_(2/3))O₃, and 0<α≦0.73.
 17. A dielectric composition for high frequencies as claimed in claim 11, wherein said Ba(M^(II) _(1/3) M^(v) _(2/3))O₃ is Ba(Zn_(1/3) Ta_(2/3))O₃, and 0<α≦0.76.
 18. A dielectric composition for high frequencies as claimed in claim 12, wherein said glass is MgO-BaO-B₂ O₃ -SiO₂ --based glass which contains 20-50% by weight of MgO, 5-25% by weight of BaO, 15-30% by weight of B₂ O₃, and 10-25% by weight of SiO₂, and said glass is added to said ceramic component at a rate of 2-30% by weight. 